Beta cyclopentadienyl hydrazides and carbazates

ABSTRACT

Beta tetrachlorocyclopentadienyl alpha methyl hydrazide, having the formula C5Cl4NNHCOCH3, is a fungicide, and can be prepared by room temperature reaction of acetic anhydride (or a tertiary amine and acetyl chloride) with C5Cl4NNH2. Chloroformate esters permit formation of similar carbazates. Selected substituents on the cyclopentadienyl group and/or on the group attached to the carbonyl group are identified. Such compounds have biological activity, particularly as a foliar fungicide and/or as a soil fungicide.

United States Patent Dixon et al.

May 6, 1975 BETA CYCLOPENTADIENYL HYDRAZIDES AND CARBAZATES Inventors: Dale D. Dixon, Kutztown; Joseph V.

Urenovitch, Allentown, both of Pa.

Air Products and Chemicals, Inc., Philadelphia, Pa.

Filed: Sept. 9, 1970 Appl. No.: 70,883

Assignee:

US. Cl. 260/468 E; 260/454; 260/468 J; 260/514 .1; 260/518 A; 260/558 H; 260/561 Int. Cl C071: 125/00 Field of Search 260/468 E, 479

References Cited UNITED STATES PATENTS 1/1969 Well 260/463 10/1912 Ley etal 260/557 OTHER PUBLICATIONS Smith, Open Chain Nitrogen Compounds, p. 163 (1966).

Primary Examiner-Robert Gerstl Attorney, Agent, or Firml.eroy Whitaker; Everet F. Smith 5 7 ABSTRACT Beta tetrachlorocyclopentadienyl alpha methyl hydrazide, having the formula c chNNncocm, is a fungicide, and can be prepared by room temperature reaction of acetic anhydride (or a tertiary amine and acetyl chloride) with C Cl NNI-l, Chloroformate esters permit formation of similar carbazates. Selected substituents on the cyclopentadienyl group and/or on the group attached to the carbonyl group are identified. Such compounds have biological activity, particularly as a foliar fungicide and/or as a soil fungicide.

2 Claims, No Drawings BETA CYCLOPENTADIENYL HYDRAZIDES AND CARBAZATES BACKGROUND OF THE INVENTION Those skilled in the art would ordinarily expect hydrazones having less than 6 carbon atoms to be soluble in dilute acid. However. tetrachlorocyclopentadienone hydrazone is insoluble even in concentrated hydrochloric acid according to H. Disselnkotter, Agnew Chem (1 ntl. Ed.) 3 (No. 5), 379 (I964). Disselnkotter also noted that it did not react with aldehydes or ketones thus distinguishing tetrachlorocyclopentadienone hydrazone from conventional hydrazones. The inertness of this hydrazone has tended to discourage its investigation.

SUMMARY OF THE INVENTION In accordance with the present invention, a cyclopentadienone hydrazone is reacted with an acid halide or acid anhydride to provide a carbazate or a hydrazide. It is convenient to employ Y to designate the cyclopentadienone group, so that the hydrazone is Y NNH wherein X is independently selected from fluorine, chlorine, bromine, and hydrogen. The acid chloride is represented by OCOX, in which Q designates a substituted or unsubstituted hydrocarbyl radical ofa hereinafter designated class. A chloroformate ester QCOX in which 0 is an alkoxy radical reacts similarly to an acid chloride. An acid anhydride can be designated as (QCOhO. Internal anhydrides (sometimes called cyclic anhydrides) such as maleic anhydride or phthalic anhydride can be designated as Z(CO) O in which Z partakes of the nature of O-Q while still partaking of the nature of Q. In order to embrace internal anhydrides, linear anhydrides, chloroformate esters, and acid halides. the term A designates all four so that QCOA designates the four types of carbonyl reactants. Thus the generic reaction is:

YNNH QCOA YNNHCOQ HA The Q of the desired product YNNHCOQ or o x x I NNHCQ LII g. Meta-dinitrophenyl radical, and

h. C,C alkoxy radicals.

The carbazates are represented by the YNNHCOO compounds in which O is a C -C alkoxy radical. The hydrazides are represented by the YNNHCOO compounds in which O is selected from (a) through (g) above.

Certain described novel compounds have been found by the present invention to possess biological activity, particularly as foliar fungicides and/or as soil fungicides.

Certain of the compounds can be prepared by the reaction of YNNI-I with OCOA in which Q has the designation heretofore given and A identifies a member of the group consisting of halide, linear anhydride component, and cyclic anhydride component. The presence of a proper amount of tertiary amine capable of reacting with hydrogen halide by-product is desirable when a chloroformate ester or an acid halide is employed. YNNH can also be reacted with linear acid anhydrides in the absence of any tertiary amine, but a catalytic or even stoichiometric amount of tertiary amine is generally not harmful in using linear acid anhydrides. Surprisingly the cyclic anhydrides cannot be readily reacted with tetrahalocyclopentadienone hydrazone unless catalytic amounts (e.g., 10% of stoichiometric amounts) of a tertiary amine are present.

DESCRIPTION OF A FEW PREFERRED EMBODIMENTS The invention is further clarified by reference to a plurality of examples.

The preferred synthetic method features the reaction of tetrachlorocyclopentadienone hydrazone with a suitable halide of the substituent to be attached to the alpha nitrogen of the hydrazone. Great care must be exercised in the synthesis because of the propensity of the products and/or reactants to undergo polymerization and/or hydrolysis reactions. If appropriate precautions are taken, then the compounds of the present invention may be prepared by any of the appropriate series of steps for combining several moieties of the compounds to prepare YNNI-ICOQ.

EXAMPLE I An Erlenmeyer flask (500 ml.) containing 200 ml. of dry tetrahydrofuran is provided with a stirrer. The reactants, l0.0 grams (0.043 mol.) of tetrachlorocyclopentadienone hydrazone, 3.4 grams (0.043 mol.) of acetyl chloride, and 4.5 grams (0.043 mol.) of triethyl amine were added (one reactant being added dropwise) and the crude solution was filtered to separate the hydrochloride salt of triethylamine. In similar reactions, pre vious workers have generally indicated the desirability of heating to reflux, and thereafter cooling the mixture prior to the separation of the salt. By reason of the ease of decomposition of the product in its synthesis environment, the synthesis and preliminary isolation of product were conducted without heating. The tetrahydrofuran solvent was removed from the filtrate by controlled vacuum treatment. The residual material was dissolved in hot methanol and the solution cooled to provide recrystallized product. The compound C CI NNHCOCH melted at l38l40C. and its elemental analysis was reasonably consistent with the expected compound as indicated in the following analytical results for alpha acetyl beta tetrachlorocyclopentadienyl hydrazide C H CI N O.

It was noted that C Cl NNHCOCl-l killed 92% of the late blight tomato (LBT) and 7l% of the leaf rust wheat (LRW) when the standard aqueous spray treatment solution contained only 75 ppm of the alpha CALCULATED FOUND 5 methyl beta tetrachlorocyclopentadienyl hydrazide. At a concentration of 30 ppm. 76% of the LBT was killed. 5 ?:22 ?:22 In the standard procedure for evaluating the foliar N 10.22 mm fungicidal effectiveness of a candidate compound, a group of plants was placed upon a turntable which was l0 rotated to i receive evaluated controlled amount of The Compound C5Cl4NNHCOCHa YNNH- aqueous spray. The fungicidal activity was evalulated COMe) was dissolved in solution which was a suitable by determining the whcemmtion f a sompound in the solvent (acetone, methanol, ethanol or other) and the aqueous Spray which ld produce a i ifi t f i solution was dispersed in deionized water containing cida] ff t wetting and dispersing agents to provide an aqueous so- 15 lution. The solution did not damage any plants in the EXAMPLES fungicidal testing, so no tabulation thereof was neces- F u i h genera procedure f E 1 n- 01- The Percentage 0f killing of the fungus was ous beta tetrachlorocyclopentadienyl hydrazides and as a measure of the fungi'lldal effectivenes$- carbazates were prepared as indicated in Table I.

TABLE I ELEMEITAL ANALYSIS CALCULATED m2 Q M. P. C H N C H N 1 CH 138-0140 30.69 1. l6 10.22 29.90 1.8" 10.03 2 -CH C1 135-136 27.20 0.98 9.10 26.81 1.05 1.0.2 3 1 122-12 4 22.10 0.29 7. |2 2"."8 0.66 9.2 4 4 Cl l l|?l'lCl'l 112 28.90 1.8 1 7.35 28.82 1.92 7.22

5- -C|li -CHCH 89-85" 32.20 2.08 8.3 1 32.3 2 O l 8. 49

7. Cl-l OCH 118-115 31.58 1.97 9.20 20.02 1.7 9-8 8. -Cl'l 0Cl l -Cll ll6117 3 l.00 2.50 8.80 33.82 2.3" 8.93 9. -CH OCH CH CH IUD-102 36.19 3.15 8. l l 35. 11 3.07 8. 1 1 10. 0Cli 130-131 28.96 1.38 9.65 29.10 1. 42 9.86 11. 8 -CH 1131l l 31.63 1.98 99.23 31.96 2.00 9. 3 1 12. -O(CH CH 89-90" 33.96 2.51 8.80 33.88 2. 4 4 8.65

CH l3. O-CH 159160 33.96 2.51 8.80 33.81 2.39 8.60

1. OCH -CH-CH 101 38.20 1.90 8.90 38.19 1.81 9.06

O 15. Cll l ZOCl'l 128-l29 32.60 1.80 8.50 3 4.51 2- 7-93 16. -CH Br 152-151 23.80 0.09 7.93 23.71 0.7 4 7.89 17. -CH -S-C N 1 l5-1 48 29.05 0.92 12.72 2 1.22 0.90 12.71 18. CH-Cl'l 92-9 l 26.20 1.36 7.65 29.3" 1.25 1A3 B! n -cn c 98-100" 29.73 1.55 8.68 3 1. m 8.82 23 -Cll Cli -CH 121-123 35.50 2.58 9.30 36.06 2.77 9.23

/CH 21. -ca IOU-101 35.68 2.6 9.27 35. 9 2 1 7 CH 22. 3-Cll 152-153 38.00 3.93 8.86 38.11 3 05 9- 23. ((.l-l Cl-l 99100 38.00 3. 43 8.36 37.91 3A3 9.01

CH 2. -CH -Cl'l 116117 38.00 3. 13 8.85 37.90 3.13 8.65

TABLE 1 continued ELFMENTAI. twin/sis CALCULATED mum) Q M. P L l N c H v ca 3 25. CBr' 1 -1 16 28. w 1.5 7. 5 28.93 1.86 7.27

26. -(CH2)3-CH3 a l-65 36.20 3.01 8. 36.22 3.08 8. 43

27. -o(ca -cn 5o-51 0.02 3.92 7.78 10.16 3.03 7.8M

28. -0-Cll ll2-ll3 2.60 2.20 7.66 I2.78 2.15 7.6 4 29. -D- 16B-169 0.90 1.71 7.95 11.09 1.6 7 8.06 30- 1 43-1 45" 113.02 1.50 8.36 40.36 1.72 8.01 31. -Br 138-1 t0 3 4.00 0.12 6.75 32.78 1.07 7.

The chloroformic esters employed to prepare the carbazates of Examples 10-14. 26-29 are not conventional acid chlorides. but under the specified reaction conditions (room temperature, tertiary amine type of acid acceptor and inert solvent) they fit within the scope of the QCOA of the generic formula.

INTRODUCTION TO ACID ANHYDRIDE ROUTE Another preferred synthetic method requires the preparation of tetrachlorocyclopentadienone hydrazone and its reaction with an acid anhydride in an inert solvent taking care to prevent exposure of the reaction mixture to undue heat or alkalinity.

EXAMPLE 34 ness as a fungicide, 300 ppm killing 92% of LBT. 67% of LRW, and 52% of BLST (bacterial leaf spot tomato).

EXAMPLE 35 Cyclic anhydrides differ from anhydrides such as (F CCO) O in that they require the presence of at least some tertiary amine for reaction at room temperature. A 500 ml. round bottom flask contained 250 anhydrous tetrahydrofuran, to which inert solvent was added 6.4g (0.043 mole) phthalic anhydride, [0.0g (0.043 mole) tetrachlorocyclopentadienone hydrozone and 4.4g (0.043 mole) triethylamine. The solution was stirred for l5 minutes. The tetrahydrofuran was removed to provide a brown oil. Extraction of the brown oil with 100 ml of 20% hydrochloric acid removed the triethylamine and provided a brown powder which was recrystallized from ethanol to provide alpha (2-carboxy phenyl)-beta tetrachlorocyclopentadienyl hydrazide having a melting point of 229230C. The compound was effective both as a soil fungicide and as a foliar fungicide.

EXAMPLES 36 38 Following the general procedures illustrated by Example 34 or 35, various beta tetrachlorocyclopentadienyl hydrazides were prepared as indicated in Table ll.

TABLE II {LLJWFNIAL ANALYST? LLCULA'TFZD l lll') L i M 2 c 1-1 N c H V W '1 3 4. -cuc1 lob-106 2 4.55 0.59 8.20 2 4.67 0.61 8.12

o I c-oH 22s-230 a1 .10 1 .5a 7. 3s :1 30 1 m 7 H6 i 37. Cil=CH-C-OH nut-1 5 33. 2 a. 5 1 2 33. 63 1 2 1 8.52

01 I21 "1 38. =c-c OH 131-133 27. 3 0 .5 7. 05 27.56 0 63 7.15

FUNGlClDAL EFFECTlV EN ESS The fungicidal activity of the compounds was established by evaluation of effectiveness in protectant control of the growth of fungus. In the reports relating to such effectiveness, the numbers indicate the fungicidal activity was noted. The numbers indicate the percentage of killing of the fungus. In all tests the damage to the plants was not detectable. and accordingly no tabulation thereof was necessary. The concentrations were in parts per million (ppm The varieties of fungus were reported as follows:

Fungus Code late bli ht tomato LBT LEAF LIST WHEAT LRW bacterial leaf spot tomato BLST Data concerning illustrative members of the group are shown in the table entitled Fungicidal Effectiveness.

FUNGICIDAL EFFECTIVENESS Example ppm LBT LRW BLST Continued FUNGICIDAL EFFECTlVENESS Example ppm LBT LRW BLST it x o II NNHCQ l x x wherein each X is independently selected from F, Cl. Br and l and wherein Q is a C -C alkoxy radical.

2. The compound of claim 1 wherein each X is Cl and Q is methoxy.

i I t i l 

1. COMPOUND CORRESPONDING TO A STRUCTURE
 2. The compound of claim 1 wherein each X is Cl and Q is methoxy. 